CN101598912A

CN101598912A - Method for producing toner and toner

Info

Publication number: CN101598912A
Application number: CNA2009101426852A
Authority: CN
Inventors: K·周; M·N·V·麦杜加尔; E·G·奇沃茨; K·A·莫法特; P·J·格罗瓦
Original assignee: Xerox Corp
Current assignee: Xerox Corp
Priority date: 2008-06-06
Filing date: 2009-06-05
Publication date: 2009-12-09
Anticipated expiration: 2029-06-05
Also published as: US8084180B2; JP5448583B2; KR20090127229A; CN101598912B; KR101489698B1; EP2131246A1; BRPI0901995A2; EP2131246B1; US20090305159A1; MX2009005789A; JP2009294655A

Abstract

The present invention relates to method for producing toner and toner.Toner-particle is provided, in embodiments its can comprise have at least a vibrin and colorant, the nuclear of optional wax and optional other adjuvant and comprise the shell on nuclear of high molecular amorphous polyester resin.Any crystallized polyurethane resin during high molecular amorphous polyester resin in the shell can prevent to examine migrates to toner surface.

Description

Method for producing toner and toner

Technical field

[0001] present disclosure relates to the toner that is applicable to electronic photographing device.

Background technology

[0002] many methods are in preparation toner those skilled in the art's cognitive range.Emulsion aggregation method (EA) is a kind of such method.These toners can form by colorant is assembled with the latex polymer that is formed by emulsion polymerization.For example, US 5,853, and 943 relate to a kind of semi-continuous emulsion polymerizing method, are used for preparing latex by at first forming seed polymer.

[0003] utilized amorphous and crystallized polyurethane resin to prepare the ultralow fusing point of polyester EA (ULM) toner.Some of these toners have poor charged characteristic, and this may move to the surface owing to the crystalline resins component in agglomeration process.Amorphous resin also can be by crystalline resins plasticising, and this may cause the adhesion of difference.Attempted a kind of nuclear-shell side method, wherein can add the shell that comprises linear amorphous resin and come encapsulation of crystalline-amorphous compound substance; But still need to improve charged and adhesion.

Summary of the invention

[0004] present disclosure provides the toner-particle with nuclear-shell structure, and shell comprises the high molecular amorphous polyester resin.In embodiments, the method for producing toner and toner of present disclosure can comprise toner-particle, described toner-particle comprises and comprises at least a crystalline resins and one or more optional ingredients such as colorant, optional wax and the nuclear of combination thereof, with the shell on this nuclear, this shell comprises that weight-average molecular weight is about 10,000 to about 5,000,000 high molecular amorphous polyester resin.

[0005] in other embodiments, the method for producing toner and toner of present disclosure can comprise toner-particle, this toner-particle comprises and comprises at least a amorphous resin, at least a crystallizing polyester resin and one or more optional ingredients such as colorant, optional wax and the nuclear of combination thereof, with the shell on this nuclear, this shell comprises that weight-average molecular weight is about 10,000 to about 1,000,000 high molecular amorphous polyester resin.

[0006] in other embodiments, the method for producing toner and toner of present disclosure can comprise toner-particle, this toner-particle comprises and comprises at least a amorphous resin, at least a crystalline resins and one or more optional ingredients such as colorant, optional wax and the nuclear of combination thereof, with the shell resin that comprises the high molecular amorphous polyester resin, described high molecular amorphous polyester resin comprises that weight-average molecular weight is about 10,000 to about 5, poly-(propoxylated bisphenol is the fumarate altogether) of 000,000 following formula:

Wherein m can be for about 10 to about 5000, and second kind of vibrin

Wherein b can be for about 5 to about 2000, d can for about 5 to about 2000 and wherein the high molecular amorphous polyester resin with about 30wt% of shell to the amount of about 90wt% exist and second kind of resin with about 10wt% of shell extremely the amount of about 70wt% exist.

The accompanying drawing summary

[0007] Fig. 1 describes to compare the curve of the difference of rheological with the toner of the production of resins of present disclosure with the toner of producing with control resin.

Embodiment

[0008] present disclosure provides the toner-particle with excellent chargeding performance.Toner-particle has nuclear-shell structure, has the high molecular amorphous polyester resin in shell.The glass transition temperature of the toner-particle of present disclosure (Tg) is higher than the toner-particle that has the low-molecular-weight amorphous resin in the shell.As used herein, the high molecular amorphous polyester resin can have the weight-average molecular weight greater than about 10,000, and the low-molecular-weight amorphous polyester resin can have the weight-average molecular weight than high molecular amorphous resin low about 20%.Therefore the toner-particle of present disclosure can have improved toner adhesion.

[0009] any latex resin can be used to form the toner cores of present disclosure.This resin and then can make by any suitable monomers.Can select employed any monomer, depend on the concrete polymkeric substance that will use.

[0010] appropriate resin also can comprise the potpourri of amorphous polyester resin and crystallized polyurethane resin, as US 6,830, described in 860.In embodiments, resin can be formed by emulsion polymerization.

[0011] in embodiments, resin can be for by making the vibrin of glycol and diacid reaction formation in the presence of optional catalyzer.Aliphatic series and or aromatic diol can be for example with resin about 40 to about 60mol%, about in embodiments 42 to about 55mol%, about in embodiments amount of 45 to about 53mol% is selected, with alkaline metal sulfo group-aliphatic diol can with resin about 0 to about 10mol%, about in embodiments amount of 1 to about 4mol% is selected.

[0012] crystalline resins can be for example with the toner component about 5 to about 50wt%, about in embodiments amount of 5 to about 35wt% exists.Crystalline resins can have various fusing points, and for example about 30 ℃ to about 120 ℃, about in embodiments 50 ℃ to about 90 ℃.Crystalline resins can have by for example about 1 of gel permeation chromatography (GPC) mensuration, 000 to about 50,000, about in embodiments 2,000 to about 25,000 number-average molecular weight (Mn) and by for example about 2,000 to about 100 of the gel permeation chromatography that uses polystyrene standards, 000, about in embodiments 3,000 to about 80,000 weight-average molecular weight (Mw).The molecular weight distribution of crystalline resins (Mw/Mn) can be for example about 2 to about 6, about in some embodiments 2 to about 4.

[0013] amount of the organic diol of Xuan Zeing can change, and can be for example with resin about 40 to about 60mol%, in embodiments with resin about 42 to about 55mol%, about 45 to about 53mol% the amount with resin exists in embodiments.

[0014] this catalyzer can be with for example extremely amount use of about 5mol% of about 0.01mol%, based on the initial diacid or the diester that are used to generate vibrin.

[0015] resin that is used to form nuclear can have by the gel permeation chromatography (GPC) that uses polystyrene standards measure about 1000 to about number-average molecular weight (M of 1,000,000, about in embodiments 2000 to about 500,000 _n) and about 2000 to about weight-average molecular weight (M of 3,000,000, about in embodiments 4,000 to about 1,500,000 _w).

[0016] in embodiments, the resin that uses in the nuclear can have about 35 ℃ to about 100 ℃, about in some embodiments 40 ℃ to about 80 ℃ glass transition temperature.In other embodiments, the resin that uses in the nuclear can have about 130 ℃ about 10 to about 1,000,000Pa*S, about in embodiments 20 to about 100, the melt viscosity of 000Pa*S.

[0017] can use a kind of, two or more toner resins.Use therein in the embodiment of two or more toner resins, toner resin can be any suitable ratio (for example weight ratio), and for example about 10% (first kind of resin)/90% (second kind of resin) is to about 90% (first kind of resin)/10% (second kind of resin).

[0018] above-mentioned resin can be used for forming method for producing toner and toner.This method for producing toner and toner can comprise optional colorant, wax and other adjuvant.Toner can utilize any method in those skilled in the art's cognitive range to form.

[0019] in embodiments, being used for forming colorant, wax and other adjuvant of method for producing toner and toner can be for comprising the dispersion form of surfactant.In addition, toner-particle can be formed by the emulsion aggregation method, and wherein other component of resin and toner places one or more surfactants, forms emulsion, gathering, coalescent toner-particle, and optionally washing and drying, and reclaim.

[0020] can use a kind of, two or more surfactants.Surfactant can be selected from ionic surface active agent and non-ionic surfactant.Anionic surfactant and cationic surfactant are contained by term " ionic surface active agent ".In embodiments, can use surfactant make its with about 0.01wt% of method for producing toner and toner to about 5wt%, for example about 0.75wt% is to about 4wt%, about in embodiments 1wt% is the amount existence of about 3wt% extremely.

[0021] as the colorant that adds, various known suitable colorants, for example the potpourri of dyestuff, pigment, dye mixture, pigment composition, dyestuff and pigment etc. can be included in the toner.Colorant can with for example toner about 0.1 to about 35wt%, or about 1 to about 15wt%, or about amount of 3 to about 10wt% is included in the toner.

[0022] optional, in forming toner-particle, wax also can with resin and coloring material for mixing.When comprising, wax can be with about 1wt% of for example toner-particle to about 25wt%, and about in embodiments 5wt% is the amount existence of about 20wt% extremely.

[0023] wax that can select comprises having for example about 500 waxes to about weight-average molecular weight of 20,000, about in embodiments 1,000 to about 10,000.

[0024] toner-particle can be by any method preparation in those skilled in the art's cognitive range.Though followingly describe the embodiment of producing about toner-particle according to the emulsion aggregation method, can use any appropriate method for preparing toner-particle, comprise chemical method, US5 for example, disclosed suspension and envelope in 290,654 and 5,302,486.In embodiments, method for producing toner and toner and toner-particle can be by assembling and the preparation of coalescent method, and it is the appropriate toner granularity that wherein undersized resin particle is assembled, toner-particle shape and form that coalescent then acquisition is final.

[0025] in embodiments, method for producing toner and toner can be prepared by the emulsion aggregation method, for example comprise choosing wantonly and in above-mentioned surfactant, assemble optional colorant, optional wax and adjuvant any other hope or required, and the potpourri that comprises the emulsion of above-mentioned resin, coalescent then aggregation potpourri.Can prepare potpourri by add the colorant also can choose wantonly in comprising the dispersion of surfactant and optional wax or other material in emulsion, described emulsion can be the potpourri of two or more emulsions of containing resin.The pH of gained potpourri can be with sour, for example adjusting such as acetate, nitric acid.In embodiments, the pH of potpourri can be adjusted to about 4 to about 5.In addition, in embodiments, potpourri can be by homogenizing.If potpourri is by homogenizing, homogenizing can be by being realized to about 4,000 rev/mins of mixing with about 600.Homogenizing can be realized by any suitable device, comprise for example IKA ULTRA TURRAX T50 probe homogenizer.

[0026] aggregating agent prepared therefrom can be for example with about 0.1wt% of resin in the potpourri to about 8wt%, about in embodiments 0.2wt% is about 5wt% extremely, the about in other embodiments 0.5wt% extremely amount of about 5wt% joins in the potpourri that is used to form toner.Provide sufficient amount of reagent for gathering like this.

[0027] in order to control agglomeration of particles and coalescent, in embodiments, can in time aggregating agent prepared therefrom be metered in the potpourri.For example, can through about 30 to about 200 minutes reagent be metered in the potpourri in embodiments through about 5 to about 240 minutes, although can according to hope maybe needs use more or less time.The adding of reagent also can remain on stirring with potpourri, be that about 50rpm is to about 1 in embodiments, 000rpm, in other embodiment is that about 100rpm is to about 500rpm, temperature with the glass transition temperature that is lower than above-mentioned resin, be about 30 ℃ to about 90 ℃ in embodiments, extremely in about 70 ℃ of following times, carry out to be about 35 ℃ in embodiments.

[0028] can allow particle aggregation and/or coalescent, up to obtaining predetermined desired particle size.Before being illustrated in and forming, measures predetermined required size the desired particle size that obtains and up to reaching the granularity of monitoring during the growth course before this granularity.Can sample during the growth course and for example analyze particle mean size with the Ku Leerte counter.Therefore can be by keeping high temperature, or lentamente temperature is increased to for example about 40 ℃ to about 100 ℃, and potpourri was remained on this temperature about 0.5 hour to about 6 hours, about in embodiments 1 hour to about 5 hours, keep to stir simultaneously assemble/coalescent, so that the particle of gathering to be provided.In case reach predetermined desired particle size, suspend growth course then.In embodiments, Yu Ding desired particle size is in above-mentioned toner particle size range.

[0029] adding the aggregating agent prepared therefrom growth and the shaping of particle afterwards can realize under any suitable condition.For example, increase and be shaped can assemble therein with the coalescent condition that takes place respectively under carry out.For gathering that separates and agglomeration step, accumulation process can be at for example about 40 ℃ to about 90 ℃, carry out under about in embodiments 45 ℃ of shearing conditions to about 80 ℃ high temperature, and described high temperature can be lower than the glass transition temperature of above-mentioned resin.

[0030] is focused to after the desired particle size, particle then can be coalescent to required net shape, coalescent for example by with mixture heated to being in or being higher than about 65 ℃ to about 105 ℃ of plexiglas transition temperature, about in embodiments 70 ℃ to about 95 ℃ temperature, and/or stirring is elevated to for example about 400rpm to about 1,000rpm, about in embodiments 500rpm extremely about 800rpm realize.Can use higher or lower temperature, should understand temperature is a function that is used for the resin of base-material.Coalescent can be at about 0.1 to about 9 hours, finish in about in embodiments 0.5 to about 4 hours.

[0031] assemble and/or coalescent after, potpourri can be cooled to room temperature, for example about 20 ℃ to about 25 ℃.As required, cooling can be rapidly or slowly.Suitable cooling method can comprise to introduce cold water in the chuck of reactor.After the cooling, can choose wantonly and wash toner-particle with water, dry then.Dry can the realization by any suitable drying means comprises for example freeze drying.

[0032] in embodiments, after assembling but before coalescent, can apply shell to the particle of assembling.As mentioned above, in embodiments, the resin that is used to form shell can be the high molecular amorphous polyester resin.This resin can comprise any of above-mentioned amorphous resin as nuclear, if this resin have as measure by the gel permeation chromatography (GPC) that uses polystyrene standards about 5,000 to about 1,000,000, about in embodiments 15,000 to about 500,000 number-average molecular weight (M _n) and about 10,000 to about 5,000,000, about in embodiments 10,000 to about weight-average molecular weight (M of 1,000,000, about in other embodiments 20,000 to about 1,000,000 _w).

[0033] in embodiments, the high molecular amorphous polyester resin can have about 2 to about polydispersity (M of 8, about in embodiments 3 to about 6 _w/ M _n).Though often use Narrow Molecular Weight Distribution usually, in the embodiment of present disclosure, can use bread molecular weight distribution.In some embodiments, the high molecular amorphous polyester resin has big polydispersity, for example at least about 3, is at least about 5 in embodiments.Can use big polydispersity to guarantee lower glass transition temperatures (Tg), but in the high viscosity that is higher than amorphous polyester resin under the about 5 ℃ temperature of Tg.

[0034] in embodiments, the high molecular weight resin that is used to form shell can be linear resin.For example, in embodiments, the high molecular weight resin that is used to form shell can be poly-(propoxylated bisphenol-be total to-fumarate) of following formula:

Wherein m can be about 10 to about 5000.

[0035] in embodiments, the high molecular amorphous polyester resin that uses in the shell can have about 40 ℃ to about 100 ℃, about in embodiments 50 ℃ to about 80 ℃ glass transition temperature.In other embodiments, the high molecular amorphous polyester resin can have about 130 ℃ about 50 to about 1,000,000Pa*S, in embodiments about 130 ℃ about 100 to about 100, the melt viscosity of 000Pa*S.

[0036] the high molecular amorphous polyester resin that uses in the shell can have and is higher than about 100 ℃, about in embodiments 100 ℃ to about 200 ℃, about in other embodiments 110 ℃ to about 150 ℃ softening point.The softening point that is used for the high molecular amorphous polyester resin of shell can be taller and bigger in about 50 ℃ than the agglomerated temperature that is used to form toner-particle in embodiments, in embodiments than high about 50 ℃ to about 100 ℃ of the agglomerated temperature that is used to form toner-particle.

[0037] difference that has the softening point that the toner of low-molecular-weight resin compares with the toner that has high molecular weight resin in shell in shell can be about 5 ℃ to about 100 ℃, is about 10 ℃ to about 50 ℃ in embodiments, depends on the resin of use.

[0038] the high molecular amorphous polyester resin that is used to form shell can use separately, and perhaps in embodiments, the high molecular amorphous polyester resin can combine with other amorphous resin and form shell.In embodiments, the high molecular amorphous polyester resin can be with about 20wt% of whole shell resins to about 100wt%, in embodiments with about 30wt% of whole shell resins extremely the amount of about 90wt% exist.Therefore, in embodiments, second kind of resin can be with about 0wt% of whole shell resins to about 80wt%, in embodiments with about 10wt% of shell resin extremely the amount of about 70wt% be present in the shell resin.

[0039] in embodiments, the molecular weight of high molecular amorphous polyester resin can be than the molecular weight height of amorphous resin in the nuclear at least about 20% in the shell of present disclosure toner, in embodiments than the molecular weight high about 20% of amorphous resin in the nuclear to about 1000%, in embodiments than the molecular weight high about 50% to about 500% of amorphous resin in the nuclear.

[0040] in the shell of present disclosure toner the viscosity of high molecular amorphous polyester resin can about 130 ℃ down than the viscosity height of amorphous resin in examining at least about 50%, in embodiments about 130 ℃ down than nuclear in the viscosity high about 50% of amorphous resin to about 500%, in embodiments about 130 ℃ down than the viscosity height about 80% to about 200% of amorphous resin in examining.

[0041] shell that uses the high molecular amorphous resin to form thus can have about 50nm to about 2 μ m, and about in embodiments 200nm is to the thickness of about 1 μ m.

[0042] the shell resin can be applied to the particle of gathering by any method in those skilled in the art's cognitive range.In embodiments, the shell resin can be in comprising the emulsion of above-mentioned any surfactant.The particle of above-mentioned gathering can combine with described emulsion, makes the high molecular amorphous polyester resin form shell on the aggregation that forms.

Therefore [0043] toner-particle with shell of present disclosure can have about 3 μ m to about 15 μ m, and about in embodiments 4 μ m are to the size of about 12 μ m and about 30 ℃ to about 80 ℃, about in embodiments 35 ℃ of about 65 ℃ glass transition temperatures extremely.

[0044], just can the pH regulator of potpourri be arrived about 3 to about 10 and about in embodiments 5 to about 9 value with alkali in case obtain required toner-particle final size.Regulate pH and can be used for freezing, also promptly stop the toner growth.The alkali that is used to stop the toner growth can comprise any suitable alkali, for example alkali metal hydroxide, for example NaOH, potassium hydroxide, ammonium hydroxide, its combination etc.In embodiments, can add ethylenediamine tetraacetic acid (EDTA) helps pH regulator to above-mentioned desirable value.

[0045] compare with the lower molecular weight vibrin, the high molecular amorphous polyester resin that is used to form shell can have low acid number.Though low acid number usually corresponding to the chargeding performance of difference, finds to have the charged characteristic that the toner of the present disclosure of high molecular amorphous polyester resin and low acid number has excellence surprisingly in shell.The acid number that is used to form the resin of nuclear can be for about 5 to about 100mL KOH/g polymkeric substance, be about 10 to about 50mLKOH/g polymkeric substance in embodiments, and the acid number that is used to form the resin of shell can be for about 5 to about 100mLKOH/g polymkeric substance, is about 10 to about 40mL KOH/g polymkeric substance in embodiments.

[0046] because the amorphous polyester resin that is used to form shell has higher molecular weight, the viscosity of expression shell is higher, so any crystalline resins of high molecular amorphous resin in preventing to examine migrates to toner surface.In addition, the high molecular amorphous polyester resin may be more incompatible with the crystalline resins that is used to form nuclear, and this may cause higher toner glass transition temperature (Tg), and therefore can obtain improved adhesion and charged characteristic.In addition, the toner that has the present disclosure of high molecular amorphous polyester resin in shell can show the excellent stained performance characteristic of document.Though do not wish to be subjected to any theory constraint, the viscosity higher that it is believed that high molecular weight polyester resins in the shell may be the reason of giving above-mentioned desirable characteristics to toner-particle.

[0047] in embodiments, toner-particle also can according to hope maybe needs contain other optional adjuvant.For example, toner can comprise the plus or minus charge control agent, and for example amount is about 0.1 to about 10wt% of toner, be in embodiments toner about 1 to about 3wt%.The example of suitable charge control agent comprises quaternary ammonium compound, comprises the halogenated alkyl pyridine; Hydrosulfate; The alkyl pyridine compound comprises US 4,298, those disclosed in 672; Organo-sulfate and sulphonic acid ester composition comprise US 4,338, those disclosed in 390; Cetyl pyridinium tetrafluoro boric acid ester; Methylsulfuric acid distearyl Dimethyl Ammonium; Aluminium salt, for example BONTRON E84 ^TMOr E88 ^TM(Hodogaya Chemical); Its combination etc.This charge control agent can apply simultaneously or apply after applying the shell resin with above-mentioned shell resin.

[0048] also can comprise the external additive particle that helps the stream adjuvant with the toner-particle blend, this adjuvant may reside on the surface of toner-particle.The example of these adjuvants comprises metal oxide, for example titanium dioxide, monox, tin oxide, its potpourri etc.; Colloidal silica and amorphous silica, for example

The slaine of slaine and fatty acid comprises zinc stearate, aluminium oxide, ceria and composition thereof.Each of these external additives can be with about 0.1wt% of toner to about 5wt%, in embodiments with about 0.25wt% of toner extremely the amount of about 3wt% exist.Suitable adjuvant comprises US 3,590, those disclosed in 000,3,800,588 and 6,214,507.Equally, these adjuvants can apply simultaneously or apply after applying the shell resin with above-mentioned shell resin.

[0049] in embodiments, the toner of present disclosure can be used as ultralow fusing point (ULM) toner.In embodiments, dry toner-particle does not comprise external surface additive, can have following characteristic:

[0050] (1) volume mean diameter (being also referred to as " volume average particle size ") is about 3 to about 25 μ m, is about 4 to about 15 μ m in embodiments, is about 5 to about 12 μ m in other embodiments.

[0051] (2) number average physical dimension distribute (GSDn) and/or the equal physical dimension of body distribute (GSDv) be about 1.05 to about 1.55, be about 1.1 to about 1.4 in some embodiments.

[0052] (3) circularity is about 0.9 to about 0.99 (with for example Sysmex FPIA 2100 analysis-e/or determinings).

[0053] characteristic of toner-particle can be measured by any suitable technology and equipment.The equal particle diameter D of body _50v, GSDv and GSDn can utilize the surveying instrument according to the manufacturer specification operation, for example Beckman Coulter Multisizer 3 measures.Representative sample can followingly carry out: can obtain and filter the about 1 a small amount of toner sample that restrains via 25 microns screen clothes, join then and obtain about 10% concentration, test sample in Beckman Coulter Multisizer 3 then in the isotonic solution.

[0054] when being exposed to extreme relative humidity (RH) condition, can have the charged characteristic of excellence according to the toner of present disclosure production.Low humidity zone (C zone) is about 10 ℃/15%RH, and high humidity regions (a-quadrant) is about 28 ℃/85%RH.The toner of present disclosure also can have the parent toner charge unit mass of extremely about-35 μ C/g of pact-3 μ C/g than the final toner charge of-5 μ C/g after (Q/M) and the blend surface additive to about-50 μ C/g.

[0055] according to present disclosure, the charged of toner-particle can be enhanced, and therefore may need surface additive still less, and final thus toner is charged can be higher to satisfy the charged requirement of machine.

[0056] toner-particle can be prepared becomes developer composition.Toner-particle can mix with carrier granular and obtains the two-component developing agent composition.Toner concentration in the developer can for about 1wt% of developer general assembly (TW) to about 25wt%, be about 2wt% about 15wt% extremely of developer general assembly (TW) in embodiments.

[0057] carrier granular of Xuan Zeing can use being with or without under the situation of coating.In embodiments, carrier granular can comprise the nuclear that has coating on it, and described coating can be formed by the not tight approaching polymeric blends of triboelectric series.

[0058] in embodiments, PMMA can choose wantonly and any required comonomer copolymerization, as long as the gained multipolymer keeps suitable granularity.Suitable comonomer can comprise monoalkyl or dialkylamine, for example dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, methacrylic acid diisopropylaminoethyl ethyl ester or t-butylaminoethyl methacrylate etc.Can by with carrier core with based on the coating carrier granular weight about 0.05 to about 10wt%, about in embodiments polymer mixed of 0.01 to about 3wt% is adhered to carrier core up to polymkeric substance by mechanical presses and/or electrostatic attraction and prepares carrier granular.

[0059] various effective appropriate method can be used for polymkeric substance is applied on the carrier core particle surface, and for example the cascade roller mixes, overturns, mills, shakes, the spraying of electrostatic powder cloud, fluidized bed, electrostatic disc processing, static curtain, its combination etc.Carrier core particle and mixture of polymers can be heated then, make polymkeric substance can fusion and consolidation to the carrier core particle.The carrier granular of coating can cool off then and be categorized as desired particle size thereafter.

[0060] in embodiments, the carrier that is fit to can comprise that size is for example for about 25 to about 100 μ m, be of a size of about 50 in embodiments to about 75 μ m, use US 5,236,629 and 5,330, to about 10wt%, about in embodiments 0.7wt% is to the steel nuclear of the conducting polymer potpourri coating of about 5wt% with about 0.5wt% for the method for describing in 874, and described conducting polymer potpourri comprises for example methyl acrylate and carbon black.

[0061] carrier granular can with toner-particle with various suitable combined hybrid.Concentration can for about 1wt% of method for producing toner and toner to about 20wt%.But different toners and carrier number percent can be used for obtaining having the developer composition of desirable characteristics.

[0062] toner can be used for electrofax or xerox method, comprises US 4,295, those disclosed in 990.In embodiments, can in image developing apparatus, use the image enhancement system of any known type, comprise that for example magnetic brush development, transition single component development, hydridization do not have the development of removing (HSD) etc.These and similar toning system are in those skilled in the art's cognitive range.

[0063] imaging process comprises for example with the xerox device construction drawing picture that comprises charged assembly, image-forming assembly, photoconductive assembly, developing device, transfer printing assembly and consolidation assembly.In embodiments, developing device can comprise the developer by mixed carrier and the preparation of said method for producing toner and toner.The xerox device can comprise high-speed printer (HSP), black and white high-speed printer (HSP), color printer etc.

[0064] in case via suitable image developing method, for example said method is any, forms image with toner/developer, and then this image just can be transferred to image receiver media, for example on the paper etc.In embodiments, toner can be in developed image in the image developing apparatus of use consolidation roller element.Consolidation device in consolidation roller element contact those skilled in the art cognitive range, wherein heat and the pressure from roller can be used for making the toner consolidation to image receiver media.In embodiments, be molten to image receive on the base material after or during, the consolidation element can be heated to the temperature higher than toner melting temperature, for example be heated to about 70 ℃ to about 160 ℃, be heated to about 80 ℃ to about 150 ℃ in embodiments, be heated to about 90 ℃ to about 140 ℃ in other embodiments.

[0065] toner resin is in the crosslinkable embodiment therein, this crosslinked can the realization in any suitable manner.For example, when toner resin under melting temperature during crosslinkable, toner resin can be crosslinked during the base material in the toner consolidation.For example in the consolidation operation of back, the crosslinked influence that also may be subjected to the image of consolidation is heated to uniform temperature, toner resin will take place crosslinked under this temperature.In embodiments, crosslinked can in embodiments at about 70 ℃ to about 160 ℃, carrying out to about 140 ℃ temperature at about 80 ℃ in other embodiments at about 160 ℃ or lower.

Embodiment

Comparative Examples 1

[0066] the about 397.99 linear amorphous resins of gram (about 17.03wt% resin) with emulsion form join in 2 liters of beakers.Linear amorphous resin has following formula:

Wherein m is about 5 to about 1000, and described linear amorphous resin is according to US 6,063, and the step of describing in 827 is synthetic, and its disclosure all is incorporated herein by reference.About 74.27 grams of emulsion form are had the unsaturated crystalline polyester (" UCPE ") (about 19.98wt% resin) that the potpourri by ethylene glycol and dodecanedioic acid and fumaric acid comonomer of following formula is formed:

Wherein b is 5 to 2000, d is 5 to 2000, and described unsaturated crystallized polyurethane resin is synthetic according to the step of describing among the US2006/0222991, and its disclosure all is incorporated herein by reference, with about 29.24 gram green pigments, pigment blue 15: 3 (about 17wt%) add in the beaker.Under homogenizing, by mixing this potpourri with about 3000 to 4000rpm, with the Al of about 36 grams ₂(SO ₄) ₃(about 1wt%) adds as flocculating agent.

[0067] potpourri is transferred in 2 liters of Buchi reactors subsequently, is heated to about 45.9 ℃ and is used for assembling, mix with the speed of about 750rpm.With Ku Leerte counter monitoring granularity, reach the average external volume granularity of about 6.83 μ m and about 1.21 physical dimension distribution (" GSD ") up to granularity.Add about 198.29 grams then and have the above-mentioned emulsion of formula I resin in particle, form shell on particle, making particle have particle mean size is about 8.33 μ m, and GSD is about 1.21 core/shell structure.

, by add NaOH the pH of reaction paste be increased to about 6.7, add about 0.45pph EDTA (based on the toner of drying) subsequently and freeze, also promptly end toner and grow [0068] thereafter.After ending the toner growth, reaction mixture is heated to about 69 ℃ and remain on this temperature and be used for coalescent in about 1 hour.

[0069] the gained toner-particle has the final average external volume granularity of about 8.07 μ m and about 1.22 GSD.

[0070] the toner slurry is cooled to room temperature then, separates and filtration by screen cloth (utilizing 25 μ m screen clothes), subsequently washing and freeze drying.

Embodiment 1

[0071] the about 397.99 linear amorphous resins of gram (about 17.03wt% resin) with emulsion form join in 2 liters of beakers.Linear amorphous resin has following formula:

Wherein m is about 5 to about 1000.With unsaturated CPE resin emulsion (formula IV) (about 19.98wt% resin) and the about 29.24 gram green pigments of about 74.27 grams from above Comparative Examples 1, pigment blue 15: 3 (about 17wt%) join in the beaker.Under homogenizing, by mixing this potpourri with about 3000 to about 4000rpm, with the Al of about 36 grams ₂(SO ₄) ₃(about 1wt%) adds as flocculating agent.

[0072] potpourri is transferred in 2 liters of Buchi reactors subsequently, is heated to about 45.5 ℃ and is used for assembling, mix with the speed of about 750rpm.With Ku Leerte counter monitoring granularity, reach the average external volume granularity of about 6.97 μ m and about 1.25 GSD up to granularity.

[0073] about 149.48 grams of emulsion form have with the high molecular amorphous resin of resin same structure formula (formula I) as nuclear and add as shell.

[0074] be used for Comparative Examples 1 shell the low-molecular-weight amorphous resin and be used for difference between the high molecular amorphous resin of shell of embodiment 1 and sum up and be summarized in following table 1; The difference of the rheological of the toner that the high molecular amorphous resin that uses in low-molecular-weight amorphous resin that uses in the shell by Comparative Examples 1 and the shell of embodiment 1 produces is summed up in the accompanying drawings.

Table 1

Amorphous resin in the shell	Mw	Mn	Acid number (mLKOH/g polymkeric substance)	Softening point ℃	Initial Tg ℃
Amorphous resin in the shell	Mw	Mn	Acid number (mLKOH/g polymkeric substance)	Softening point ℃	Initial Tg ℃	Low Mw resin (Comparative Examples 1)	12.5	4.4	16.7	107	56.7
High Mw resin (embodiment 1)	38.8	6.4	12	123	62	Low Mw resin (Comparative Examples 1)	12.5	4.4	16.7	107	56.7

[0075] measures the acid number proof and have acid moieties, and measure acid number by the Titrable acid group.Acid number be in and the milligram number of the required potassium hydroxide of the free acid of 1 gram in the resin.

[0076] the high molecular amorphous resin forms shell on the nuclear particle of above generation, obtains having the average external volume granularity and be about 8.15 μ m and GSD and be the particle of about 1.23 core/shell structure.

, by add NaOH the pH of reaction paste be increased to about 6.1, add about 0.45pph EDTA (based on the toner of drying) subsequently and freeze, also promptly end toner and grow [0077] thereafter.After ending the toner-particle growth, reaction mixture is heated to about 69 ℃ and remain on this temperature and be used for coalescent in about 7 hours.

[0078] the gained toner-particle has the final average external volume granularity of about 8.07 μ m and about 1.25 GSD.

[0079] the toner slurry is cooled to room temperature then, separates and filtration by screen cloth (utilizing 25 μ m screen clothes), subsequently washing and freeze drying.

[0080] with as the toner of producing in the Comparative Examples 1 that in shell, has the low-molecular-weight amorphous resin compares, show remarkable improvement in A district and C district aspect charged as the toner that in shell, has the high molecular amorphous resin produced among the embodiment 1, as by all blowing out (blow off) equipment, also claim what the Barbetta box was measured.Developer is nursed one's health in A and C district and is spent the night, and uses paint shaker charged about 5 to about 60 minutes then, provides and relevant with the stability of the developer between the zone in time information.Have in shell that the toner of embodiment 1 of high molecular weight resin is same to show improved relative humidity sensitivity, keep simultaneously with Comparative Examples 1 in have the identical form of toner of low-molecular-weight resin in the shell of production.The data that the high molecular amorphous resin that uses in low-molecular-weight amorphous resin that uses in the shell according to Comparative Examples 1 and the shell of embodiment 1 obtains are summed up and are summarized in the following table 2.

Table 2

Q/M=unit of charge mass ratio

28 ℃/the 85%RH in AZ=A district

10 ℃/the 15%RH in CZ=C district

5M-PS=5 minute short developer electrification time

60M-PS=60 minute longer developer electrification time

[0081] the consolidation characteristic of the toner that produces among Comparative Examples 1 and the embodiment 1 also by wrinkle area, minimum fixing temperature, glossiness, document is stained and the stained test of vinyl is measured.

[0082] result who obtains according to the toner of Comparative Examples 1 and embodiment 1 is summarized in the following table 3.

Table 3

The minimum fixing temperature of MFT=(toner takes place to accept bonding minimum temperature to mounting medium)

The Xerox paper that DCX=is uncoated

The Xerox paper of DCEG=coating

The gram number that gsm=is every square metre

CA=wrinkle area

T _G40=reach the melting temperature of 40 glossiness units

[0083] from table 3 as seen, use the high molecular amorphous resin to improve 24 hours stained performances of document of toner as shell.The visible serious toner of the toner of Comparative Examples 1 destroys SIR=1.00/1.25 to toner (15.1 gram) and toner to paper (12.5 gram).On the contrary, the toner grade that has the embodiment 1 of high molecular amorphous resin in the shell is SIR=2.00 (toner is to toner, and 0.23 restrains) and SIR=1.75 (toner is to paper, and 0.92 restrains).

[0084] in shell, use the high molecular amorphous resin also to make wrinkle photographic fixing MFT _CA=85Be offset to higher temperature: temperature from about 140 ℃ (Comparative Examples 1) to about 148 ℃ (embodiment 1) on uncoated paper nuclear, on coated paper, observe similar trend.

Therefore, at this following embodiment is disclosed.

1. 1 kinds of method for producing toner and toner that comprise toner-particle of scheme comprise:

Comprise that at least a crystalline resins and one or more are selected from the nuclear of the optional member of colorant, optional wax and combination thereof; With

Comprise that weight-average molecular weight is the shell of about 10,000 to about 5,000,000 high molecular amorphous polyester resin.

Scheme 2. is according to the method for producing toner and toner of scheme 1, and its center further comprises amorphous resin.

Scheme 3. is according to the method for producing toner and toner of scheme 1, and wherein crystalline resins is selected from polyester, polyamide, polyimide, polyolefin, ethylene-propylene copolymer, vinyl-vinyl acetate copolymer and combination thereof.

Scheme 4. is according to the method for producing toner and toner of scheme 1, wherein crystalline resins comprises and is selected from following polyester: poly-(hexane diacid second diester), poly-(hexane diacid propylene diester), poly-(hexane diacid fourth diester), poly-(hexane diacid penta diester), poly-(the own diester of hexane diacid), poly-(the hot diester of hexane diacid), poly-(succinic acid second diester), poly-(succinic acid propylene diester), poly-(succinic acid fourth diester), poly-(succinic acid penta diester), poly-(the own diester of succinic acid), poly-(the misery diester of amber), poly-(decanedioic acid second diester), poly-(decanedioic acid propylene diester), poly-(butylene sebacate), poly-(decanedioic acid penta diester), poly-(the own diester of decanedioic acid), poly-(the hot diester of decanedioic acid), alkaline metal copolymerization (5-sulfo group isophthaloyl)-copolymerization (hexane diacid second diester), alkaline metal copolymerization (5-sulfo group isophthaloyl)-copolymerization (hexane diacid propylene diester), alkaline metal copolymerization (5-sulfo group isophthaloyl)-copolymerization (hexane diacid fourth diester), alkaline metal copolymerization (5-sulfo group isophthaloyl)-copolymerization (hexane diacid penta diester), alkaline metal copolymerization (5-sulfo group isophthaloyl)-copolymerization (the own diester of hexane diacid), alkaline metal copolymerization (5-sulfo group isophthaloyl)-copolymerization (the hot diester of hexane diacid), alkaline metal copolymerization (5-sulfo group isophthaloyl)-copolymerization (hexane diacid second diester), alkaline metal copolymerization (5-sulfo group isophthaloyl)-copolymerization (hexane diacid propylene diester), alkaline metal copolymerization (5-sulfo group isophthaloyl)-copolymerization (hexane diacid fourth diester), alkaline metal copolymerization (5-sulfo group isophthaloyl)-copolymerization (hexane diacid penta diester), alkaline metal copolymerization (5-sulfo group isophthaloyl)-copolymerization (the own diester of hexane diacid), alkaline metal copolymerization (5-sulfo group isophthaloyl)-copolymerization (the hot diester of hexane diacid), alkaline metal copolymerization (5-sulfo group isophthaloyl)-copolymerization (succinic acid second diester), alkaline metal copolymerization (5-sulfo group isophthaloyl)-copolymerization (succinic acid propylene diester), alkaline metal copolymerization (5-sulfo group isophthaloyl)-copolymerization (succinic acid fourth diester), alkaline metal copolymerization (5-sulfo group isophthaloyl)-copolymerization (succinic acid penta diester), alkaline metal copolymerization (5-sulfo group isophthaloyl)-copolymerization (the own diester of succinic acid), alkaline metal copolymerization (5-sulfo group isophthaloyl)-copolymerization (the misery diester of amber), alkaline metal copolymerization (5-sulfo group isophthaloyl)-copolymerization (decanedioic acid second diester), alkaline metal copolymerization (5-sulfo group isophthaloyl)-copolymerization (decanedioic acid propylene diester), alkaline metal copolymerization (5-sulfo group isophthaloyl)-copolymerization (butylene sebacate), alkaline metal copolymerization (5-sulfo group isophthaloyl)-copolymerization (decanedioic acid penta diester), alkaline metal copolymerization (5-sulfo group isophthaloyl)-copolymerization (the own diester of decanedioic acid), alkaline metal copolymerization (5-sulfo group isophthaloyl)-copolymerization (the hot diester of decanedioic acid), alkaline metal copolymerization (5-sulfo group isophthaloyl)-copolymerization (hexane diacid second diester), alkaline metal copolymerization (5-sulfo group isophthaloyl)-copolymerization (hexane diacid propylene diester), alkaline metal copolymerization (5-sulfo group isophthaloyl)-copolymerization (hexane diacid fourth diester), alkaline metal copolymerization (5-sulfo group isophthaloyl)-copolymerization (hexane diacid penta diester), alkaline metal copolymerization (5-sulfo group isophthaloyl)-copolymerization (the own diester of hexane diacid) and poly-(the hot diester of hexane diacid), wherein alkaline metal comprises and is selected from sodium, the metal of lithium and potassium.

Scheme 5. is according to the method for producing toner and toner of scheme 1, and its center further comprises and is selected from following amorphous resin: polyester, poly-(cinnamic acrylic ester) resin, crosslinked poly-(cinnamic acrylic ester) resin, poly-(styrene-methacrylate) resin, crosslinked poly-(styrene-methacrylate) resin, poly-(styrene-butadiene) resin, crosslinked poly-(styrene-butadiene) resin, the vibrin of alkaline metal sulfonation, the polyimide resin of alkaline metal sulfonation, the polyimide resin of alkaline metal sulfonation, poly-(cinnamic acrylic ester) resin of alkaline metal sulfonation, poly-(cinnamic acrylic ester) resin of crosslinked alkaline metal sulfonation, poly-(styrene-methacrylate) resin, poly-(styrene-methacrylate) resin of crosslinked alkaline metal sulfonation, poly-(styrene-butadiene) resin of alkaline metal sulfonation, poly-(styrene-butadiene) resin and the combination thereof of crosslinked alkaline metal sulfonation.

Scheme 6. is according to the method for producing toner and toner of scheme 1, and its center further comprises poly-(propoxylated bisphenol-be total to-fumarate) resin of following formula:

Wherein m can be about 5 to about 1000.

Scheme 7. is according to the method for producing toner and toner of scheme 1, and wherein the high molecular amorphous polyester resin is selected from polyester, poly-(cinnamic acrylic ester) resin, crosslinked poly-(cinnamic acrylic ester) resin, poly-(styrene-methacrylate) resin, crosslinked poly-(styrene-methacrylate) resin, poly-(styrene-butadiene) resin, crosslinked poly-(styrene-butadiene) resin, the vibrin of alkaline metal sulfonation, the polyimide resin of alkaline metal sulfonation, the polyimide resin of alkaline metal sulfonation, poly-(cinnamic acrylic ester) resin of alkaline metal sulfonation, poly-(cinnamic acrylic ester) resin of crosslinked alkaline metal sulfonation, poly-(styrene-methacrylate) resin, poly-(styrene-methacrylate) resin of crosslinked alkaline metal sulfonation, poly-(styrene-butadiene) resin of alkaline metal sulfonation, poly-(styrene-butadiene) resin and the combination thereof of crosslinked alkaline metal sulfonation.

Scheme 8. is according to the method for producing toner and toner of scheme 1, and wherein the high molecular amorphous polyester resin comprises poly-(propoxylated bisphenol-be total to-fumarate) of following formula:

Wherein m can be for about 10 to about 5000, and wherein the high molecular amorphous polyester has about 10,000 to about weight-average molecular weight of 1,000,000.

Scheme 9. is according to the method for producing toner and toner of scheme 1, wherein the high molecular amorphous polyester resin exists to the amount of about 100wt% with about 20wt% of shell resin, have about 40 ℃ to about 100 ℃ glass transition temperature, about 100 ℃ to about 200 ℃ softening point, with at 130 ℃ of following about 50Pa*S extremely about 1,000, the melt viscosity of 000Pa*S.

Scheme 10. is according to the method for producing toner and toner of scheme 1, wherein toner-particle has the size of about 3 μ m to about 15 μ m, compare with the toner that does not have the high molecular amorphous polyester resin in the shell, have higher A district electric charge and wherein this toner-particle have about 35 ℃ to about 65 ℃ glass transition temperature.

Scheme 11. is according to the method for producing toner and toner of scheme 1, the molecular weight height at least 20% of amorphous resin in the molecular weight ratio of the amorphous polyester resin nuclear in its mesochite, in 130 ℃ of lower casings in the viscosity ratio of the amorphous polyester resin nuclear viscosity height at least 50% of amorphous resin and its mesochite have the extremely thickness of about 2 μ m of about 50nm.

12. 1 kinds of method for producing toner and toner that comprise toner-particle of scheme comprise:

Comprise that at least a amorphous resin, at least a crystallizing polyester resin and one or more are selected from the nuclear of the optional member of colorant, optional wax and combination thereof; With

Comprise that weight-average molecular weight is the shell of about 10,000 to about 1,000,000 high molecular amorphous polyester resin.

Scheme 13. is according to the method for producing toner and toner of scheme 12, at least a amorphous resin in its center is selected from polyester, poly-(cinnamic acrylic ester) resin, crosslinked poly-(cinnamic acrylic ester) resin, poly-(styrene-methacrylate) resin, crosslinked poly-(styrene-methacrylate) resin, poly-(styrene-butadiene) resin, crosslinked poly-(styrene-butadiene) resin, the vibrin of alkaline metal sulfonation, the polyimide resin of alkaline metal sulfonation, the polyimide resin of alkaline metal sulfonation, poly-(cinnamic acrylic ester) resin of alkaline metal sulfonation, poly-(cinnamic acrylic ester) resin of crosslinked alkaline metal sulfonation, poly-(styrene-methacrylate) resin, poly-(styrene-methacrylate) resin of crosslinked alkaline metal sulfonation, poly-(styrene-butadiene) resin of alkaline metal sulfonation, poly-(styrene-butadiene) resin of crosslinked alkaline metal sulfonation and combination thereof and at least a crystalline resins are selected from polyester, polyamide, polyimide, polyolefin, ethylene-propylene copolymer, vinyl-vinyl acetate copolymer and combination thereof.

Scheme 14. is according to the method for producing toner and toner of scheme 12, and wherein the high molecular amorphous polyester resin comprises poly-(propoxylated bisphenol-be total to-fumarate) of following formula:

Wherein m can be for about 10 to about 5,000, wherein the high molecular amorphous polyester resin have about 40 ℃ to about 100 ℃ glass transition temperature, about 100 ℃ to about 200 ℃ softening point, with down about 50Pa*S are extremely about 1,000 at 130 ℃, the melt viscosity of 000Pa*S.

Scheme 15. is according to the method for producing toner and toner of scheme 12, wherein the crystallizing polyester resin is selected from poly-(hexane diacid second diester), poly-(hexane diacid propylene diester), poly-(hexane diacid fourth diester), poly-(hexane diacid penta diester), poly-(the own diester of hexane diacid), poly-(the hot diester of hexane diacid), poly-(succinic acid second diester), poly-(succinic acid propylene diester), poly-(succinic acid fourth diester), poly-(succinic acid penta diester), poly-(the own diester of succinic acid), poly-(the misery diester of amber), poly-(decanedioic acid second diester), poly-(decanedioic acid propylene diester), poly-(butylene sebacate), poly-(decanedioic acid penta diester), poly-(the own diester of decanedioic acid), poly-(the hot diester of decanedioic acid), alkaline metal copolymerization (5-sulfo group isophthaloyl)-copolymerization (hexane diacid second diester), alkaline metal copolymerization (5-sulfo group isophthaloyl)-copolymerization (hexane diacid propylene diester), alkaline metal copolymerization (5-sulfo group isophthaloyl)-copolymerization (hexane diacid fourth diester), alkaline metal copolymerization (5-sulfo group isophthaloyl)-copolymerization (hexane diacid penta diester), alkaline metal copolymerization (5-sulfo group isophthaloyl)-copolymerization (the own diester of hexane diacid), alkaline metal copolymerization (5-sulfo group isophthaloyl)-copolymerization (the hot diester of hexane diacid), alkaline metal copolymerization (5-sulfo group isophthaloyl)-copolymerization (hexane diacid second diester), alkaline metal copolymerization (5-sulfo group isophthaloyl)-copolymerization (hexane diacid propylene diester), alkaline metal copolymerization (5-sulfo group isophthaloyl)-copolymerization (hexane diacid fourth diester), alkaline metal copolymerization (5-sulfo group isophthaloyl)-copolymerization (hexane diacid penta diester), alkaline metal copolymerization (5-sulfo group isophthaloyl)-copolymerization (the own diester of hexane diacid), alkaline metal copolymerization (5-sulfo group isophthaloyl)-copolymerization (the hot diester of hexane diacid), alkaline metal copolymerization (5-sulfo group isophthaloyl)-copolymerization (succinic acid second diester), alkaline metal copolymerization (5-sulfo group isophthaloyl)-copolymerization (succinic acid propylene diester), alkaline metal copolymerization (5-sulfo group isophthaloyl)-copolymerization (succinic acid fourth diester), alkaline metal copolymerization (5-sulfo group isophthaloyl)-copolymerization (succinic acid penta diester), alkaline metal copolymerization (5-sulfo group isophthaloyl)-copolymerization (the own diester of succinic acid), alkaline metal copolymerization (5-sulfo group isophthaloyl)-copolymerization (the misery diester of amber), alkaline metal copolymerization (5-sulfo group-isophthaloyl-copolymerization (decanedioic acid second diester), alkaline metal copolymerization (5-sulfo group-isophthaloyl)-copolymerization (decanedioic acid propylene diester), alkaline metal copolymerization (5-sulfo group-isophthaloyl)-copolymerization (butylene sebacate), alkaline metal copolymerization (5-sulfo group-isophthaloyl)-copolymerization (decanedioic acid penta diester), alkaline metal copolymerization (5-sulfo group-isophthaloyl)-copolymerization (the own diester of decanedioic acid), alkaline metal copolymerization (5-sulfo group-isophthaloyl)-copolymerization (the hot diester of decanedioic acid), alkaline metal copolymerization (5-sulfo group-isophthaloyl)-copolymerization (hexane diacid second diester), alkaline metal copolymerization (5-sulfo group isophthaloyl)-copolymerization (hexane diacid propylene diester), alkaline metal copolymerization (5-sulfo group isophthaloyl)-copolymerization (hexane diacid fourth diester), alkaline metal copolymerization (5-sulfo group isophthaloyl)-copolymerization (hexane diacid penta diester), alkaline metal copolymerization (5-sulfo group isophthaloyl)-copolymerization (the own diester of hexane diacid) and poly-(the hot diester of hexane diacid)

Wherein alkaline metal comprises the metal that is selected from sodium, lithium and potassium.

Scheme 16. is according to the method for producing toner and toner of scheme 12, and its mesochite further comprises the second kind of resin that exists to the amount of about 70wt% with about 10wt% of shell, and high molecular weight resin with about 30wt% of shell extremely the amount of about 90wt% exist.

Scheme 17. is according to the method for producing toner and toner of scheme 12, and its mesochite has the thickness of about 50nm to about 2 μ m.

Scheme 18. is according to the method for producing toner and toner of scheme 12, wherein toner-particle has the size of about 3 μ m to about 15 μ m, compare with the toner that does not have the high molecular amorphous polyester resin in the shell, have higher A district electric charge and have about 35 ℃ to about 65 ℃ glass transition temperature.

19. 1 kinds of method for producing toner and toner that comprise toner-particle of scheme comprise:

Comprise that at least a amorphous resin, at least a crystalline resins and one or more are selected from the nuclear of the optional member of colorant, optional wax and combination thereof; With

The shell resin that comprises high molecular amorphous polyester resin and second kind of vibrin, described high molecular amorphous polyester resin comprise that the weight-average molecular weight of following formula is about 10,000 to about 5,000,000 poly-(propoxylated bisphenol-be total to-fumarate):

Wherein m can be for about 10 to about 5000, and described second kind of vibrin is

Wherein b can for about 5 to about 2000 and d can be for about 5 to about 2000,

With

Wherein the high molecular amorphous polyester resin with about 30wt% of shell to the amount of about 90wt% exist and second kind of resin with about 10wt% of shell extremely the amount of about 70wt% exist.

Scheme 20. is according to the method for producing toner and toner of scheme 19, wherein the high molecular amorphous polyester resin have about 40 ℃ to about 100 ℃ glass transition temperature, about 100 ℃ to about 200 ℃ softening point, with at 130 ℃ of following about 50Pa*S extremely about 1,000, the melt viscosity of 000Pa*S and

Wherein toner-particle has about 3 μ m to the size of about 15 μ m, compares with the toner that does not have the high molecular amorphous polyester resin in the shell, has higher A district electric charge and has about 35 ℃ of about 65 ℃ glass transition temperatures extremely.

Claims

1. method for producing toner and toner that comprises toner-particle comprises:

2. according to the method for producing toner and toner of claim 1, its center further comprises amorphous resin.

3. method for producing toner and toner that comprises toner-particle comprises:

4. method for producing toner and toner that comprises toner-particle comprises:

Wherein b can for about 5 to about 2000 and d can be for about 5 to about 2000,

With